Azo dyestuff.



OFFICE.

MARSTON TAYLOR BOGERT, OFNEW YORK. N. Y.

Azo nvnsrurr.

Specification of Letters Patent. IatQnte-{l Dec; 19, 1911.

No Drawing. Application filed January 5, 1910, Serial No. 536,481. Renewed January 3, 191 1. Serial No;

T 0 all whom it may concern:

Be itknown that I, MARSTON TAYLOR Bo eERT, a citizen of ,theUnited' States, and a resident of the city of New York, borough of Manhattan, in the count-y'and State of New York, have invented certainnew and useful Improvements in Azo Dyestuii's, of which the following is such a full, clear, and accurate description as will enable any'one skilled in the art to which it appertains to make and use the same.

My invention relates to the manufacture and production of new azo dyestuffs by using quinazolin compounds as couplers to combine with various diazo or tetrazo salts.

In my application No. 487695, filed April 3,-1909,.it is shown that compounds contain.

ing the nucleus couple readily with diazo 01-" tetrazo salts,

thereby yielding new azo dyestufis. In the above formula Ar represents a simple or substituted aromatic nucleus and R represents a simple or substituted alphylorfaryl radical. I have now found that this coupling is not dependent upon the presence of the -Ar.N group of the above formula, or even of the oxygen of the CO group, but that diaz-o or tetrazo salts will unite direct with a great variety of compounds containing the quinazo'lin nucleus or skeleton B l l thereby producing new and useful azo dyestufi's, all of which contain the grouping Ar-N:N-Q inwhich Ar represents a simple or substituted aromatic nucleus, and Q the quinazolin compound used as the coupler, the 2120 group being attached to the henzole portion of the quinazolin nucleus.

When the tetrazo salt isused, disazo dyes may be produced of the Q -N NAr--N: N -X type, in which Ar-is the nucleus of the tetra-- zotized base, Q is a quinaz ohncoupler, and

X either a coupler. a

The coupling of the diazo or; tetrazo salt with a quinazolin coupler is ca'rriedout according to the well-known methods employed zolin couplers appear adapted tense in essentially the same manner as other couplers are now employed for the productionof. azo

dyestuffs.

These new azo dyestutfs maybe used. as finished dyes, or the diazotizing-and coupling may be ca rried out in the fiber itself. They may also be used as,mordant dyes; or for the preparation of pigments by using quinazolin coupler or some other .in preparing azo dyestuffs, and these quinainsoluble a'zo combinations or suitablelakes.

If the quinazolin coupler carries a di'azotizable amino group, the aminoaz'o dye obtained may beagain diazotized and coupled, thus giving a polyaz'o. dyestutf. .T hese'new azo dyestu'ifs are substantive'forsilk and wool. Many of them are also direct cotton dyes. y

The following example will further illustrate the nature of my invention and how it can be carried into practical effect, "but my invention is not limited to thisexample. The parts are by weight.

' Example: 206 parts of the sodium' salt of benzoy-lene urea (also known as QA-dihy .droxyquinazolim -0r 2A- diketotetrahydroquinazolin) are dissolved in sufficient;

ter to give a clear solution. On'e par't'of caustic soda is added, and 2-34; partsd-izvzo naphthionic acid (made into agthin paste with Water) .is slowly stirred in. After ter, it' dissolves to a reddish solutionwhich changes to a pale yellow when boiled with Zinc dust. It dissolves in glacial acetic acid to a bright red solution, and in alcohol (95%) to an orange-red one, but is practically insoluble in ether. Reduced with stannous chlorid and hydrochloric acid, an am no quinazolin is reduced in which the amino group is attac ed to the benzole pore tion' of the quinazolin nucleus. If this amino quinazolin be separated, diazot-ized and coupled with napi-tliionic acid, the dyestutf obtained is not identical with the original one.

In lieu of the naphthionic acid used in the above example, I have successfully employed many other aromatic amins and amino compounds. cate that any of the amino compounds used for the production of diazo or tetrazo salts in preparing other azodyestuflis can be used equally well with quinazolin' couplers.

In lieu of the benzoylene urea mentioned above, I have successfully employed a great many other quinazolin compounds; as, for example, i-quinaz'olone (khydroxyquinazd lin), 2-methyl-4c-quinazolone, 2-methyl-- phenyl-l-quinazolone, 2.3-dimethyl 4 quinazolone, 2-phenyll-quinazolone, 2-benzyl- 4 quinazolone, Q-methyl-fi-brom--quinazolone, 2-methyl-7-nitro-4-quinazolone, 2.3- dimethyl-o-nitrol-quinazolone, 5 amino-t quinazolone, 2'isopropyll-thioquinazolone, 3-phenyldihydroquinazolin (orexin), thiobenzoylene urea, and others. My exp-err ments would seem to show that any quinazolin compound can be used which still has a position free, on the benzole side of the nucleus, to which the diazo group can attach itself. V

My experiments'indicate that these new azo dyestuffs possess the following general properties: They are substantive dyes for sill; and Wool, many also dyeing cotton direct, They include both monazo and polyazo dyestuffs. In concentrated sulfuric acid, they dissolve to richly colored solutions, the color varyingwith the particular dyestuii used. Their solutions in concentrated hydrochloric acid are rapidly reduced and the color changed to a pale yellow by the addition of stannous chlorid, the azo groups being split between'the nitrogcns. One product of this splitting is an My experiments indi amino quinazolin in which the amino group is attached to the benzole side of the ub nazolin nucleus; but, on reduction in this Way, no one of these dyes gives both a 5- ainino quinazolin and l-amindQ-naphthol; Further, if the amino quinazolin obtained by this reduction be diazotized and coupled with the same component or components used in the preparation of the original dye, a dyestufi different "from the original one is obtained.

I employ the expression diazotized aromatic compound generically to include either the diazo or tetrazo saltand I employ the expression aromatic nucleus generically to include either a simple or substituted aromaticnucleus and I desire to cover generically both the monazo and poly azo structures.

What I claim and wish to secure by Letters Patent is 1. The process of producing azo dyestuffs by coupling a diazotizedaromatic compound with compounds containing the fob lowing quinazolin nucleus all of whichv dyestufis contain the group ArN:N-Q in which Ar is an aromatic nucleus and Q is the quinazolin coupler used. I

2. As an article of manufacture, an azo dyestufl' which contains the group Ar--N;N-Q in which Ar is an aromatic nucleus and Q is the quinazolin coupler used, and which, when reduced with stannous chlorid and hydrochloric acid gives an amido quinazolin compound in which the amido group is attached to the benzole portion of said quinazolin nucleus. y

In testimony whereof, I have hereunto signed my name in the presence of two subscribing Witnesses.

MARSTON TAYLOR BOGERT. V'Vitnesses:

ALFRED H. KRoPFF, CARL G. AMEND. 

